CN109449005B - Integrated super capacitor - Google Patents
Integrated super capacitor Download PDFInfo
- Publication number
- CN109449005B CN109449005B CN201811368813.0A CN201811368813A CN109449005B CN 109449005 B CN109449005 B CN 109449005B CN 201811368813 A CN201811368813 A CN 201811368813A CN 109449005 B CN109449005 B CN 109449005B
- Authority
- CN
- China
- Prior art keywords
- integrated
- super capacitor
- cathode
- anode
- full
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 113
- 239000007773 negative electrode material Substances 0.000 claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 88
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000002484 cyclic voltammetry Methods 0.000 claims description 30
- 239000010405 anode material Substances 0.000 claims description 27
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 26
- 239000010406 cathode material Substances 0.000 claims description 25
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000002086 nanomaterial Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010277 constant-current charging Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000011244 liquid electrolyte Substances 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 22
- 230000007246 mechanism Effects 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000002073 nanorod Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 12
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910015799 MoRu Inorganic materials 0.000 description 3
- 241000917012 Quercus floribunda Species 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to an integrated super capacitor. The concept and invention of integrating the super capacitor are put forward for the first time, and the super capacitor is characterized in that the super capacitor can be arbitrarily used as a positive electrode material and a negative electrode material of the super capacitor to be compounded or mixed according to a certain proportion, so that a single electrode voltage window of the super capacitor can work in a positive electrode area and a negative electrode area. After the electrodes of the integrated super capacitor are assembled into a full-capacitance device, the properties of the integrated super capacitor are different from the traditional symmetrical and asymmetrical full capacitors. The full capacitance of the integrated super capacitor simultaneously comprises a plurality of traditional full capacitance mechanisms, so that the full capacitance voltage window and the capacity are greatly improved. The method is simple to operate, can be applied to nano-grade materials, is also suitable for common powder particle materials, has wide application range and rich sources of optional materials, and has industrial prospect.
Description
Technical Field
The invention relates to the field of super capacitors, in particular to an integrated super capacitor.
Background
In the present society, energy and environment become two major problems facing human beings. The exhaustion of traditional energy sources such as coal, petroleum and the like and increasingly outstanding environmental pollution problems present challenges to the survival and development of human beings. In this context, some clean, economical, renewable energy sources have received a great deal of attention from scientists. Energy problems and energy storage problems are closely related, and lithium ion batteries and super capacitors are two commonly used energy storage devices. Nowadays, lithium ion batteries have been widely used in the fields of electronic devices, electric vehicles, power grids, and the like. Although the lithium ion battery has high capacity, the power density and the cycle life of the lithium ion battery cannot meet the requirements of high-power charge and discharge and ultra-long-time application. The super capacitor can be complementary to the application of the lithium ion battery, and is a device of the super lithium battery with higher energy and far-reaching power density. In the fields of electronic equipment, electronic elements, electric automobiles and the like, a super capacitor plays a crucial role, particularly in the field of electric automobiles, a single lithium battery often cannot provide high energy density in a short time, so that the capacity of high-power work such as initial starting and climbing of the electric automobiles is greatly limited, and the super capacitor can release great energy in a short time to meet the requirement. However, although the super capacitor has the advantage of high power density, the capacity of energy storage is far from the battery. In addition, the operating voltage window of the water-based supercapacitor is difficult to reach the height of the organic lithium battery due to the limitation of the theoretical voltage (1.23V) of water decomposition. Therefore, the optimization of the capacity and the working voltage interval of the super capacitor is the key point of research in the field of super capacitors.
Over decades of efforts, supercapacitors have made major advances through process approaches such as nanostructure and chemical optimization of existing materials (adv. Energy mater.2014, 4: 1300816; Energy environ.sci., 8: 702.), exploration of new materials (Nature 2014,516: 78; Science,2016,353: 1137.), optimization of electrolytes (chem. eng.j.2017, 321: 554; nat. mater.2013, 12: 351) and assembly of full capacitance (chem. soc.rev.2016, 45: 5925). Ruthenium dioxide, for example, is considered to be a superior capacitor material, but its use is limited by its expensive price. However, due to the defects of poor conductivity, poor stability and the like, most of non-noble metal oxides (such as manganese oxide, iron oxide, molybdenum oxide, nickel oxide, cobalt oxide and the like) cannot be put into commercial use. In addition, the metal oxides are often required to be made into nano-structured materials or doped with other materials in a composite way to obtain excellent performance. And the process means are usually only small-scale research in a laboratory and cannot be commercially produced at all. In addition to conductivity and stability, the voltage range of the single electrode and the full capacitance formed by these metal oxides is limited, and it is difficult for the single electrode to exceed the voltage range of 1V, and the full capacitance to exceed the potential of 1.5V. Therefore, the research and engineering efforts are directed to how to solve the capacity and voltage window problems of the conventional materials such as non-noble metals by the simplest and commercially available method.
Disclosure of Invention
Based on the foregoing background, the present invention provides an integrated supercapacitor. According to the invention, any anode material and any cathode material which can be used as a super capacitor are compounded or mixed in a certain proportion to be used as a single electrode, so that the voltage window of the obtained super capacitor single electrode can work in an anode region and a cathode region, and the working range of the electrode is greatly widened. After the two single electrodes are assembled into a full-capacitance device, the properties of the full-capacitance device are different from those of the traditional symmetrical and asymmetrical full capacitors. The full capacitance of the integrated supercapacitor can simultaneously include multiple full capacitance mechanisms to achieve a large increase in the full capacitance voltage window and capacity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
provided is an integrated supercapacitor, wherein two single electrodes of the whole capacitance of the integrated supercapacitor are the same and are obtained by combining any positive electrode material and any negative electrode material which can be used for the supercapacitor. The full capacitance obtained by the assembly has the efficiency of multiple mechanisms, and the capacitance capacity and the voltage window are greatly improved compared with the traditional symmetrical and asymmetrical capacitors.
According to the scheme, the combination mode of the positive electrode material and the negative electrode material in the single electrode of the integrated super capacitor can be that the positive electrode material and the negative electrode material are compounded through structural design or directly and simply mixed.
According to the scheme, the combination proportion of the positive electrode material and the negative electrode material meets the requirement that the capacitance capacity of the single electrode obtained by final combination in the positive electrode area and the negative electrode area is equivalent. The capacity corresponding to the capacity is a capacity within a range of 30%, preferably within 20%, more preferably within 15%, and still more preferably within 10% of the capacity of the single electrode in the positive electrode region and the capacity of the single electrode in the negative electrode region. The single electrode obtained by the method can be combined with the voltage interval of the anode and cathode materials, and has better effect when working in the positive and negative full voltage interval. Specifically, the measurement can be performed by adopting an electrochemical Cyclic Voltammetry (CV) test mode, and the optimal condition is as follows: the ratio of the areas of the positive and negative voltage regions of the cyclic voltammogram CV can be made comparable. It can also be estimated by constant current charging and discharging curve, specifically, the discharging time is equivalent in the positive and negative regions.
According to the scheme, the electrode material used for integrating the single electrode in the super capacitor is not required to be in the shape, can be a nano-grade material and can also be a common commercial powder material. The nano material can regulate the compounding ratio of the anode material and the cathode material by changing reaction time, temperature and other modes, so as to regulate the capacity ratio of the composite single electrode in the anode region and the cathode region respectively. The common powder sample can directly mix the powder of the anode and the cathode and then coat the slurry on the electrode by the traditional coating process, and the capacitance capacity ratio of the single electrode obtained by the combination in the anode and the cathode areas is regulated and controlled by the feeding ratio of the mixed anode and cathode materials.
Specifically, the single electrode can be obtained by the following method:
(1) firstly, a layer of negative electrode or positive electrode material (for example, the material is a grown array or film, and directly grows on the substrate without binder, and generally has a nano structure) grows on a conductive substrate, then another positive electrode or negative electrode material grows, finally a positive electrode material/negative electrode material compound is formed, and in the growing process, the proportion of the positive electrode material and the negative electrode material is regulated by controlling reaction time, temperature and the like.
(2) If the electrode material is a common powder sample, the anode material and the cathode material can be mixed in proportion and then coated on the surface of the conductive substrate to form a single electrode. In particular, nafion solution can be used to bind the samples. For example, mixing a nafion solution and ethanol in a volume ratio of 1:5, uniformly mixing, and coating the slurry on a conductive substrate by adopting a spin coating method; the coating method of the battery slurry process can also be adopted: the sample, conductive carbon black and vinylidene fluoride (PVDF) are mixed in a mass ratio of 8:1:1, pyrrolidone is added, the mixture is stirred into slurry, and the slurry is coated on a substrate. The cathode material and the anode material can be directly purchased or prepared by a hydrothermal method, an electrodeposition method, a physical or chemical deposition method.
The conductive substrate can be selected from titanium sheet, foamed nickel, copper sheet or carbon cloth. According to the scheme, the positive electrode material comprises the material commonly used by the super capacitorPositive electrode materials, e.g. manganese dioxide (MnO)2) Ruthenium dioxide (RuO)2) Metal oxides and hydroxides of nickel and cobalt (NiO, CoO)x,Ni(OH)2And Co (OH)2Etc.), vanadium pentoxide (V)2O5) Polypyrrole, polyaniline, and the like; the negative electrode material comprises a negative electrode material commonly used for a super capacitor, such as iron oxide (FeO)x) Vanadium Nitride (VN), molybdenum oxide (MoO)x) And tungsten oxide (WO)x) And the like.
According to the scheme, the single electrode is made of the positive electrode material with the working voltage interval of 0-1V; using a negative electrode material with a working voltage interval of-1.3-0V; the integrated single electrode working interval is-1.3-1V.
According to the scheme, the integrated supercapacitor full-capacitance structure comprises the electrolyte and the diaphragm which are arranged between two single electrodes besides the single electrodes.
According to the scheme, if the electrolyte of the integrated super capacitor is in a liquid state, the two single electrodes are separated by an NKK diaphragm or fiber paper; the liquid electrolyte adopts 1M sodium sulfate (Na)2SO4) Sulfuric acid (H)2SO4) Or potassium hydroxide (KOH) solution.
According to the scheme, if the integrated super capacitor is solid full-capacitance, the integrated super capacitor can be prepared by using polyvinyl alcohol (PVA) as a diaphragm and an electrolyte at the same time. The preparation method comprises the following steps: the preparation method comprises the following steps of (1) adding water into polyvinyl alcohol, dissolving the polyvinyl alcohol into the water to form a colloid, and directly bonding two single electrodes by using the colloid, wherein the preparation method comprises the following steps: 3-6g of polyvinyl alcohol is dissolved in 20-60ml of water at a high temperature of 70-90 ℃, is completely dissolved and adjusted into colloid, is used for directly bonding and integrating two single electrodes, and forms a solid integrated full capacitor after being naturally dried.
According to the scheme, the working voltage and the capacitance capacity of the integrated super capacitor are both higher than those of a traditional symmetrical capacitor or an asymmetrical capacitor, the working voltage interval is larger than that of a traditional full capacitor, and the capacitance capacity is more than 2-3 times higher than that of the traditional full capacitor.
The invention has the beneficial effects that:
1. the single electrode is formed by compounding any anode material and any cathode material of the super capacitor according to a certain proportion. The two single electrodes have no positive or negative component and can be used as the positive electrode or the negative electrode. After recombination, the single electrode can work in a positive electrode interval and a negative electrode interval simultaneously. Therefore, after the electrodes of the integrated capacitor are assembled into a full capacitor, the capacitor has better capacity and voltage range than the traditional symmetrical or asymmetrical capacitor due to the advantage of multiple mechanisms.
2. The integrated capacitor has low material requirement threshold no matter whether the integrated capacitor is a single electrode or a full capacitor, and almost all anode and cathode materials can achieve good efficiency in any shape combination. The method is simple to operate, can be applied to nano-grade materials, is also suitable for common powder particle materials, has wide application range and rich sources of optional materials, and has industrial prospect.
Drawings
Fig. 1(a) is a tree diagram of various conceptual relations of a supercapacitor, (b) is a voltage interval relation of an integrated single electrode and a traditional single anode or cathode, (c) is a relation between an integrated full capacitance and a traditional symmetrical or asymmetrical voltage interval and capacitance, and (d) illustrates a relation between an integrated full capacitance and a traditional capacitance mechanism by taking manganese dioxide and ferroferric oxide as an example.
FIG. 2 is an electron microscope (SEM) image of manganese dioxide nanosheets and ferroferric oxide nanorods compounded in different proportions by controlling hydrothermal for different times. Respectively is (a)0 hours (Fe)3O4) (b)5 hours (FM-5), (c)10 hours (FM-10) and (d)15 hours (FM-15).
FIG. 3(a) is CV curves of different manganese dioxide and ferroferric oxide ratios, (b) is a comparison of constant current charge-discharge curves (GCD) of ferroferric oxide alone and FM-10, and (c) is an electrochemical impedance comparison (EIS) of ferroferric oxide, manganese dioxide and FM-10.
FIG. 4 is an XRD (X-ray diffraction) spectrum of a ferroferric oxide nanorod and ferroferric oxide @ manganese dioxide.
FIG. 5(a) is the CV comparison of ferroferric oxide, manganese dioxide and integrated capacitance single electrode FM-10, (b) is the CV diagram of FM-10 under different sweep rates, (c) is the capacity under different sweep rates, (d) is the occupation ratio of capacitance mechanism, and (e) is the XRD diagram of the material under different potentials.
FIG. 6 shows the integrated full capacitance study, (a) shows CV diagrams at different voltages at 20mV/s for sweep rate, (b) shows CV diagrams at different sweep rates, (c) shows cycle performance diagrams, and inset shows comparative Rayleigh diagrams integrating capacitance and conventional capacitance, (d) to (e) shows XPS analysis of iron and manganese before and after charging and discharging, and (f) and (g) show XPS spectra of FM-N, and (h) shows changes in Raman spectra before and after charging and discharging.
FIGS. 7(a) and (b) are SEM images of molybdenum oxide of a conventional powder, and (c) is an XRD pattern of molybdenum oxide; (d) and (e) is SEM picture of common powder of ruthenium oxide, and (f) is XRD picture of ruthenium oxide; (g) and (h) is an SEM image of a common powder sample of the ferroferric oxide, and (i) is a powder sample XRD spectrum of the ferroferric oxide.
Fig. 8(a) shows CV comparison of integrated electrodes of molybdenum oxide, ruthenium oxide and MoRu, (b) GCD comparison of integrated electrodes of molybdenum oxide and MoRu, and (c) CV comparison of the fully integrated capacity of MoRu with conventional symmetrical and asymmetrical types.
Fig. 9(a) shows CV comparison of integrated electrodes of iron oxide, ruthenium oxide and FeRu, (b) GCD comparison of integrated electrodes of iron oxide and FeRu, and (c) CV comparison of FeRu integrated full capacitance and conventional symmetrical and asymmetrical types.
Detailed Description
Example 1
Performance test and mechanism proof of integrated capacitance single electrode material and integrated full capacitance of synthetic nanostructure
1) Preparing a ferroferric oxide nanorod precursor by a hydrothermal method, and calcining and reducing in hydrogen to obtain the ferroferric oxide nanorod. Specifically, 0.946g FeCl3·6H2O and 0.479g Na2SO4Dissolved in 70mL of deionized water, and then a titanium metal piece (3 cm. times.6 cm. times.0.1 mm) was put into a hydrothermal reactor and hydrothermal was carried out at 120 ℃ for 6 hours. Finally, calcination was carried out in hydrogen at 350 ℃ for 3 hours to obtain the final sample.
2) Preparing a 0.02M potassium permanganate solution, soaking the ferroferric oxide nano-rods obtained in the step 1) in the potassium permanganate solution, and respectively keeping the solution at 90 ℃ for 5 hours, 10 hours and 15 hours to obtain manganese dioxide nano-sheet composite ferroferric oxide nano-rods with different thicknesses.
Finally, the material morphology is characterized by SEM, and the material is characterized and analyzed by characterization methods such as (X-ray diffraction) XRD, Raman and X-ray photoelectron spectroscopy (XPS). And carrying out electrochemical test on the prepared single electrode in a three-electrode system of an electrochemical workstation. And finally, assembling two identical single electrodes into a liquid integrated full capacitor by adopting an NKK diaphragm and 1mol/L sodium sulfate to carry out performance test and mechanism research. The traditional symmetrical capacitor for comparison is assembled by two pieces of manganese dioxide and two pieces of ferroferric oxide respectively, and the asymmetrical full capacitor is assembled by taking manganese dioxide as a positive electrode and taking ferroferric oxide as a negative electrode.
After the ferroferric oxide and the manganese dioxide are compounded, the ferroferric oxide and the manganese dioxide can be subjected to oxidation-reduction reaction in respective voltage intervals to be connected into a whole, so that a single electrode can work in a positive electrode interval and a negative electrode interval simultaneously. After the electrodes of the integrated capacitor are assembled into a full capacitor, the integrated capacitor can comprise a traditional multiple full capacitor mechanism, and due to the multiple nature of the mechanism, the capacity and the voltage window of the integrated full capacitor are superior to those of a traditional symmetrical capacitor or an asymmetrical capacitor.
Specifically, as shown in fig. 1, fig. 1a shows a tree diagram of the conceptual relationship between the super capacitor designed by the present invention and the conventional super capacitor. The super capacitor can integrate the anode and the cathode of the traditional capacitor to form a single electrode, and after the single electrode is assembled into a full capacitor, the concept of the traditional symmetrical and asymmetrical full capacitors can be integrated. Fig. 1b is a simulated Cyclic Voltammetry (CV), and the relationship between the integrated capacitance and the conventional anode and cathode is integrated, that is, the single electrode of the integrated capacitance can achieve the purpose of working in the anode and cathode voltage regions simultaneously by the combination of the conventional anode material and cathode material, and the performance is superior to that of the single anode or cathode material. The full capacitance characteristics of the integrated capacitor are shown in fig. 1c, and the integrated full capacitor can generate a capacity and voltage operating range superior to those of the conventional symmetric and asymmetric supercapacitors. The principle is shown in fig. 1d, and a composite material of a nano-structure, namely a ferroferric oxide nanorod @ manganese dioxide nanosheet is used as an example. Manganese dioxide (MnO)2) Is a positive electrode material of a capacitor, and tetraoxideFerriferrous oxide (Fe)3O4) Is a cathode material, and when the cathode material and the anode material are integrated, the cathode material and the anode material are assembled into a full-capacitance form: fe3O4@MnO2//Fe3O4@MnO2. In practice, however, it operates by three conventional all-capacitance mechanisms: MnO2//MnO2Symmetrical, Fe3O4//Fe3O4Symmetrical, MnO2//Fe3O4Asymmetric full capacitance. It is due to the complexity of its mechanism that the integrated full capacitor has the advantage of capacity and voltage range as shown in fig. 1 c.
As shown in FIG. 2, the a picture is a ferroferric oxide nanorod structure, the surface of the ferroferric oxide nanorod structure is smooth, and the diameter of most nanorods is less than 100 nm. After 5 hours of soaking by potassium permanganate (FM-5), a thin layer of manganese dioxide nanosheet appears (b); after 10 hours (FM-10), as shown in a figure c, the manganese dioxide nano-sheets are further increased and completely cover the ferroferric oxide nano-rods; after 15 hours (FM-15), the manganese dioxide nano-sheets shown in the d picture are connected into one piece, completely cover the ferroferric oxide nano-rods, and almost no gaps exist among the nano-rods.
As shown in fig. 4, phase analysis of the obtained material by XRD, compared with a standard card, shows that the phase of the nanorod before manganese dioxide recombination is ferroferric oxide, in which a titanium-based peak also appears. After the manganese dioxide is compounded, taking FM-10 as an example, the diffraction peak of the manganese dioxide appears in the phase except for the prior ferroferric oxide, which indicates that the compounding of the manganese dioxide and the ferroferric oxide is successful.
As shown in FIG. 3, a shows CV curves of different manganese dioxide layer thicknesses, and the capacities of pure ferroferric oxide and FM-5 in the negative voltage interval are large (judged by CV area) and the capacitance of the positive electrode area is small under the sweep rate of 20 mV/s. FM-15 is larger in the positive electrode section and smaller in the negative electrode section. This is because the amount of manganese dioxide is insufficient for 5 hours or less to match with magnetite to obtain a uniform capacity over the entire region, while the amount of manganese dioxide is excessive for 15 hours, at which the positive electrode capacity is dominant. Therefore, FM-10 is the best case with comparable capacity between the positive and negative voltage regions. The graph b compares the GCD curves of pure ferroferric oxide and an integrated single electrode, and notes that the pure ferroferric oxide only has capacity in a negative electrode material and has serious voltage drop (IR drop) in a positive electrode area, which indicates that the ferroferric oxide only has the capacity in the negative electrode area and has no capacity in the positive electrode area. However, after the manganese dioxide is compounded, the integrated electrode FM-10 has capacity in the whole positive and negative regions, which shows that the integrated single electrode can achieve the effect of integrating the voltage interval of the positive and negative electrode materials. And the graph c is the EIS test comparison of the three, and shows that the charge transfer resistance of the single manganese dioxide is larger (the semi-circle size represents the charge transfer resistance), and the FM-10 resistance after the ferroferric oxide is compounded is greatly reduced to be basically close to that of the ferroferric oxide nanorod with good conductivity. This shows that the integrated capacitor has the advantages of fast charge transfer and low resistance.
As shown in FIG. 5, panel a shows CV comparison of pure ferriferrous oxide, manganese dioxide and FM-10. The comparison shows that the ferroferric oxide has good capacity (-1.3-0V) only in a negative electrode area, and the CV area is very small in a positive electrode area, which means that the capacity is very low; on the contrary, the manganese dioxide has capacity only in the positive electrode area (0-1V) and almost has no capacity in the negative electrode area, and when the potential is negative, the obvious polarization phenomenon also occurs; comparing the two, the FM-10 has capacity in the whole area (-1.3-1V) and the CV area is larger than the sum of the two. This indicates that the integrated electrode has a voltage range and capacity superior to the conventional anode or cathode alone. The graph b shows the CV curve of FM-10 at different scan rates, and the integrated capacitance still maintains a good CV shape even at a high scan rate of 1000mV/s, proving that the stability and rate capability are excellent. Graph c shows the capacitance at different sweep rates. The capacity of the integrated capacitor can reach 675F/g at a sweep rate of 5mV/s, and the capacity can still be maintained at 86F/g even at an ultrahigh sweep rate of 1000 mV/s. The ratio of the capacitive mechanism to the overall CV capacity can be calculated according to the theory of Bruce Dunn et al scientists (nat. mater.2017, 16: 454). The capacity of the available capacitive energy storage mechanism calculated by this method accounts for 85.9% of the total energy storage capacity (fig. d), and thus it can be determined that the integrated single electrode material is a material of the capacitive mechanism. In fig. d, the scanning potential of the CV can be divided into different stages to study the reaction mechanism of the integrated capacitor material, specifying the initialPotential is A1Point B when scanning to 0V, point C when continuously scanning to-1.3V, point D when returning to 0V potential, point A when closing again to 1V2And (4) point. When the potential is scanned to different positions, the research test of XRD is carried out to research the reaction process. As shown in fig. e, initially, XRD diffraction peaks were only for the first magnetite and manganese dioxide; after the potential is swept to the point B, the manganese dioxide peak disappears, and the ferroferric oxide peak is maintained, which indicates that the manganese dioxide is subjected to a reduction reaction, and the ferroferric oxide also maintains the phase; after the potential reaches the most negative C point, at the moment, the ferric oxide peak also disappears, and a new iron simple substance corresponding to the peak appears, which indicates that the ferroferric oxide is reduced into iron at the potential; when the potential returns to the point D, the ferric oxide peak appears again, and the ferric oxide peak also appears at the same time, which shows that the iron simple substance is oxidized into the ferroferric oxide and the ferric oxide in the process; finally the potential returns to A2At this point, the manganese dioxide peak reappears and the ferric oxide peak further intensifies. The analysis of the whole process can lead to the conclusion that:
A1→ B positive electrode material is reduced, Mn4+→Mn3++Mn2+ (2)
B → C that the negative electrode material is reduced, Fe3+→Fe2++Fe0,Fe2+→Fe0 (3)
C → D, oxidation of the negative electrode material, Fe2++Fe0→Fe3+ (4)
D→A2The positive electrode material is oxidized, Mn3++Mn2+→Mn4+ (5)
The reactions of the anode and the cathode are matched and continuous in the integrated capacitor, so that the anode material and the cathode material are unified finally, and the concept of the integrated capacitor is created.
As shown in FIG. 6, a is a CV diagram comparing the integrated full capacitor with the conventional full capacitor, and it can be seen that the integrated full capacitor has no obvious polarization phenomenon at a voltage of 1.8V, while the conventional symmetrical full capacitor MnO2//MnO2,Fe3O4//Fe3O4And symmetrical full-capacitance MnO2//Fe3O4The voltage is lower than 1.5V. The capacity of the integrated full capacitor is much higher than that of the conventional symmetrical and asymmetrical full capacitors according to the CV area judgment. The integrated full capacitor was subjected to CV tests at different sweep rates, as shown in graph b, where the sweep rate could even reach 5000mV/s, with slight variations in CV shape, demonstrating the stability and high rate performance of the full capacitor, which means a charge time of only 0.36 seconds. The stability test for full capacitance is shown in fig. c, which remains above 80% after 5000 cycles. The inset shows a Ravignette graph comparing the integrated full capacitor with several types of conventional full capacitor energy and power density, and it is known that the power density and energy density of the integrated full capacitor are much better than those of the conventional symmetrical type and asymmetrical type. In order to study the mechanism of the total capacitance, a single electrode connected to the positive electrode is named as FM-P, and an electrode connected to the negative electrode is named as FM-N. After the full capacitors are subjected to multiple reactions, the full capacitors are disassembled, and XPS and Raman characterization is respectively carried out on FM-P and FM-N. FIGS. d and e are XPS spectra of FM-P, and FIGS. f and g are XPS spectra of FM-N. After peak separation, tetravalent manganese (Mn)4+) Trivalent (Mn)3+) And divalent manganese (Mn)2+) The energy positions were 642.8eV, 641.3eV and at640.1eV, respectively. And ferric iron (Fe)3+) Ferrous iron (Fe)2+) And zero-valent iron (Fe)0) The energy positions are 711.4eV,709.7eV and 707.8eV, respectively. From the analysis of the d-e diagram, it can be seen that iron and manganese in FM-P tend to be in the highest valence state, whereas iron and manganese in FM-N tend to be in the lowest valence state more. This indicates that both iron oxide and manganese oxide undergo an oxidation reaction in the positive electrode and a reduction reaction in the negative electrode. Raman characterization of the h-plot further confirms this conclusion that the peaks for iron oxide and manganese dioxide in FM-N are significantly weaker than those in FM-P. Because the ferric oxide and the ferroferric oxide have close peak positions, whether the peak in FM-P is ferric oxide cannot be judged, but the I picture in the insets shows that FM-P is red in appearance, which is the typical color of ferric oxide, and FM-N is black. In conclusion, it can be shown that iron oxide and manganese oxide are more manganese dioxide and ferric oxide with the highest valence in FM-P, while FM-N isThe raman peak is weak due to the reduction of the oxide. It is deduced from the above XPS and Raman results that manganese dioxide and ferroferric oxide are involved in the chemical reactions in both electrodes, so it is reasonable to believe that there are multiple mechanisms, including MnO, therein2//MnO2Symmetrical, Fe3O4//Fe3O4Symmetrical, MnO2//Fe3O4An asymmetric all-capacitive mechanism. Therefore, the integrated full capacitor has the advantages of higher capacity and wider voltage range compared with the traditional full capacitor.
Example 2
Common commercial powder samples of molybdenum oxide and ruthenium oxide were used for the integrated capacitance study.
1) Both molybdenum oxide and ruthenium oxide powders were from common commercial powder samples. The preparation of the single electrode is simple, and the two powders are mixed in an optimal proportion (the voltage regions of the positive electrode and the negative electrode in CV area can be close to each other). After mixing, the powders were coated on a titanium substrate using the coating method described in the protocol.
2) The integrated full capacitor is assembled by two identical integrated single electrodes. The combination was the same as described in example 1.
As shown in fig. 7, the a and b are SEM images of molybdenum oxide, which shows irregular particle shape. XRD of pattern c confirmed that the powder was molybdenum oxide. The d and e plots show that ruthenium oxide is also a common particulate powder and the XRD of the f plot shows that the powder is ruthenium oxide.
As shown in fig. 8, similar to the results in example 1, molybdenum oxide as the anode material in the a diagram had capacity only in the anode region while ruthenium oxide had capacity mainly in the cathode region. After the two are mixed into an integrated capacitor, the electrode can integrate the voltage range of the two, has capacity in the whole area of-0.8V, and is larger than a single anode material or a single cathode material. The GCD curve in graph b shows that molybdenum oxide exhibits a significant voltage drop over the positive voltage interval to demonstrate that molybdenum oxide alone has no capacity over the positive voltage interval, while the integrated electrode, after integration of the positive electrode material, has capacity in both the positive and negative regions and exhibits a GCD curve typical of a triangular shape for a supercapacitor. The integrated single electrode is assembled into an integrated wholeAfter the capacitor, as shown in fig. c, the capacity and voltage range of the integrated full capacitor are much better than those of the conventional symmetrical (MoO)3//MoO3,RuO2//RuO2) And asymmetric (RuO)2//MoO3) A super capacitor.
Example 3
Common commercial powder samples of iron oxide and ruthenium oxide were used for the integrated capacitance study.
1) Both iron oxide and ruthenium oxide powders were from common commercial powder samples. The preparation of the single electrode is simple, and the two powders are mixed in an optimal proportion (the voltage regions of the positive electrode and the negative electrode in CV area can be close to each other). After mixing, the powders were coated on a titanium substrate using the coating method described in the protocol.
2) The integrated full capacitor is assembled by two identical integrated single electrodes. The combination was the same as described in example 1 and example 2.
As shown in fig. 7, the g and h plots are SEM images of iron oxide, and the morphology of the common iron oxide appears as irregular particles. XRD of the i-pattern confirmed that the powder was iron oxide.
As shown in fig. 9, similar to the results in examples 1 and 2, iron oxide as an anode material has capacity only in the anode region and ruthenium oxide has capacity mainly in the cathode region in the a diagram. After the two are mixed into an integrated capacitor, the electrode can integrate the voltage range of the two, has capacity in the whole area of-0.8V, and is larger than a single anode material or a single cathode material. The GCD curve in graph b shows that iron oxide exhibits a significant voltage drop (IR drop) in the positive voltage interval, thus demonstrating that iron oxide alone has no capacity in the positive voltage interval, while the integrated electrode has capacity in both the positive and negative regions and exhibits a GCD curve typical of a triangular shape for supercapacitors after integration of the positive electrode material. After the integrated single electrode is assembled into the integrated full capacitor, as shown in fig. c, the capacity and voltage range of the integrated full capacitor are much better than those of the conventional symmetrical type (Fe)3O4//Fe3O4,RuO2//RuO2) And asymmetric (RuO)2//Fe3O4) A super capacitor.
The above embodiment is expanded to conclude that the capacity of the single electrode in the positive voltage interval and the capacity of the negative electrode material in the negative voltage interval can be combined by combining the positive electrode material and the negative electrode material in a certain proportion, so that the single electrode can work in a wider range between the positive voltage interval and the negative voltage interval. The specific proportion of the capacity occupied by the positive voltage region and the negative voltage region can be realized by adjusting the respective amount of the composite material, and electrochemical tests are carried out after the composition to determine that the CV area is the optimal proportion when the difference between the positive voltage region and the negative voltage region is not large. After the single electrodes with the optimal proportion amount are assembled into the full capacitor, the full capacitor can realize the combination of three super capacitors of the traditional positive electrode material// positive electrode material symmetrical type, the positive electrode material// negative electrode material asymmetrical type and the negative electrode material// negative electrode material symmetrical type, thereby achieving the purpose of improving the integrated full capacitor capacity and voltage window.
Claims (8)
1. An integrated supercapacitor, comprising: the two single electrodes of the integrated super capacitor are the same and are both obtained by combining any anode material and any cathode material which can be used for the super capacitor, the combination proportion of the anode material and the cathode material meets the requirement that the capacitance capacity of the anode region and the cathode region in the continuous scanning of the anode and cathode full regions of the single electrode obtained by final combination is equivalent, the single electrode of the integrated super capacitor achieves the purpose of working in the anode voltage region and the cathode voltage region simultaneously through the combination of the anode material and the cathode material, the integrated super capacitor can realize the combination of three super capacitors of a traditional positive electrode material// positive electrode material symmetrical type, a positive electrode material// negative electrode material asymmetrical type and a negative electrode material// negative electrode material symmetrical type, so as to achieve the purpose of improving the capacity and voltage window of the integrated super capacitor, and the single electrode uses the positive electrode material with the working voltage interval of 0-1V; using a negative electrode material with a working voltage interval of-1.3-0V; the integrated single electrode working interval is-1.3-1V.
2. The integrated ultracapacitor of claim 1, wherein: and (3) estimating the equivalent capacitance by adopting an electrochemical cyclic voltammetry method based on the areas of the positive voltage region and the negative voltage region, or estimating the equivalent capacitance based on the discharge time of the positive electrode region and the negative electrode region through constant-current charging and discharging.
3. The integrated ultracapacitor of claim 1, wherein: the mode of combining the anode material and the cathode material in the single electrode of the integrated super capacitor is that the anode material and the cathode material are compounded through structural design or directly and simply mixed.
4. The integrated ultracapacitor of claim 1, wherein: the electrode material used for integrating the single electrode in the super capacitor is a nano-scale material.
5. The integrated ultracapacitor of claim 1, wherein: the single electrode is obtained by adopting the following method:
(1) firstly growing a layer of cathode or anode material on a conductive substrate, then growing another cathode or anode material to finally form a cathode material/anode material composite, and regulating and controlling the proportion of the cathode material and the anode material by adjusting and controlling reaction time and/or temperature in the growing process to enable the capacitance capacity of the cathode and the anode area of the finally combined single electrode in the whole cathode and anode areas to be equal;
(2) and mixing the positive electrode material and the negative electrode material in proportion, and coating the mixture on the surface of a conductive substrate to form a single electrode.
6. The integrated ultracapacitor of claim 1, wherein: the anode material is specifically selected from manganese dioxide, ruthenium dioxide, metal oxides and hydroxides of nickel and cobalt, vanadium pentoxide, polypyrrole and polyaniline; the negative electrode material is specifically selected from iron oxide, vanadium nitride, molybdenum oxide and tungsten oxide.
7. The integrated ultracapacitor of claim 1, wherein: the integrated super capacitor comprises an electrolyte and a diaphragm which are arranged between two single electrodes besides the single electrodes; the electrolyte of the integrated super capacitor is in a liquid state, and the two single electrodes are separated by an NKK diaphragm or fiber paper; the liquid electrolyte adopts 1M sodium sulfate, sulfuric acid or potassium hydroxide solution.
8. The integrated ultracapacitor of claim 1, wherein: the integrated super capacitor is a solid super capacitor and is prepared by using polyvinyl alcohol as a diaphragm and an electrolyte at the same time, and the preparation method comprises the following steps: after polyvinyl alcohol is dissolved in water at high temperature to be colloidal, two single electrodes are directly bonded by the polyvinyl alcohol, and the solid integrated super capacitor is formed after natural airing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811368813.0A CN109449005B (en) | 2018-11-16 | 2018-11-16 | Integrated super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811368813.0A CN109449005B (en) | 2018-11-16 | 2018-11-16 | Integrated super capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109449005A CN109449005A (en) | 2019-03-08 |
| CN109449005B true CN109449005B (en) | 2021-09-14 |
Family
ID=65554512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811368813.0A Active CN109449005B (en) | 2018-11-16 | 2018-11-16 | Integrated super capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109449005B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110335765B (en) * | 2019-07-30 | 2021-04-02 | 哈尔滨工业大学 | Method for reinforcing metal oxide supercapacitor electrode material by graphene quantum dots |
| CN113990673A (en) * | 2021-09-14 | 2022-01-28 | 北京化工大学 | Positive and negative electrode integrated Janus structure fiber aerogel and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047423A (en) * | 2015-08-07 | 2015-11-11 | 华中师范大学 | Flexible symmetrical pseudocapacitance super capacitor and preparation method thereof |
| CN105206429A (en) * | 2015-10-28 | 2015-12-30 | 武汉理工大学 | Flexible thin film electrode material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956359B (en) * | 2012-10-22 | 2015-08-19 | 太原理工大学 | A kind of manganese dioxide/ferric oxide nano composite material and its preparation method and application |
| CN105895387A (en) * | 2014-10-10 | 2016-08-24 | 南京大学 | Spherical porous Fe3O4/MnO2 supercapacitor material and preparation method thereof |
| CN104499022A (en) * | 2014-12-22 | 2015-04-08 | 西北师范大学 | Preparation and application of MnO2-SnO2/graphite nanometer array composite electrode material |
| CN105206430B (en) * | 2015-09-29 | 2017-11-03 | 南京绿索电子科技有限公司 | Polyaniline nanotube array/graphene composite material electrode and its preparation method and application |
-
2018
- 2018-11-16 CN CN201811368813.0A patent/CN109449005B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047423A (en) * | 2015-08-07 | 2015-11-11 | 华中师范大学 | Flexible symmetrical pseudocapacitance super capacitor and preparation method thereof |
| CN105206429A (en) * | 2015-10-28 | 2015-12-30 | 武汉理工大学 | Flexible thin film electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109449005A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shang et al. | Synthesis of hollow ZnCo2O4 microspheres with enhanced electrochemical performance for asymmetric supercapacitor | |
| Zhao et al. | Unravelling the reaction chemistry and degradation mechanism in aqueous Zn/MnO 2 rechargeable batteries | |
| Zhang et al. | Three-dimensional Co3O4 nanowires@ amorphous Ni (OH) 2 ultrathin nanosheets hierarchical structure for electrochemical energy storage | |
| Zhu et al. | In-situ growth of MnCo2O4 hollow spheres on nickel foam as pseudocapacitive electrodes for supercapacitors | |
| Liu et al. | Facile synthesis of NiMoO 4· x H 2 O nanorods as a positive electrode material for supercapacitors | |
| Hussain et al. | Development of vertically aligned trimetallic Mg-Ni-Co oxide grass-like nanostructure for high-performance energy storage applications | |
| Yang et al. | Facile electrodeposition of 3D concentration-gradient Ni-Co hydroxide nanostructures on nickel foam as high performance electrodes for asymmetric supercapacitors | |
| Devi et al. | Performance of bismuth-based materials for supercapacitor applications: A review | |
| Li et al. | One-dimension MnCo2O4 nanowire arrays for electrochemical energy storage | |
| Zhang et al. | Self-supported 3D layered zinc/nickel metal-organic-framework with enhanced performance for supercapacitors | |
| Lang et al. | Asymmetric supercapacitors based on stabilized α-Ni (OH) 2 and activated carbon | |
| Liu et al. | Hierarchical CuO@ ZnCo–OH core-shell heterostructure on copper foam as three-dimensional binder-free electrodes for high performance asymmetric supercapacitors | |
| Nan et al. | Hierarchical NiMn 2 O 4@ CNT nanocomposites for high-performance asymmetric supercapacitors | |
| Feng et al. | Template synthesis of a heterostructured MnO2@ SnO2 hollow sphere composite for high asymmetric supercapacitor performance | |
| Ramesh et al. | A nanocrystalline structured NiO/MnO 2@ nitrogen-doped graphene oxide hybrid nanocomposite for high performance supercapacitors | |
| CN105280394A (en) | Multilayer structure-based novel battery type supercapacitor with high power density and high energy density and preparation method | |
| Yang et al. | 3D hierarchical ZnCo2S4@ Ni (OH) 2 nanowire arrays with excellent flexible energy storage and electrocatalytic performance | |
| Ren et al. | Hierarchically nanostructured Zn0. 76C0. 24S@ Co (OH) 2 for high-performance hybrid supercapacitor | |
| CN109449005B (en) | Integrated super capacitor | |
| Tian et al. | Facile synthesis of Ni-Co layered double hydroxide with nitrates as interlayer anions via an oxidation-induced anion intercalation process for hybrid supercapacitors | |
| Pappu et al. | Electrodeposited manganese oxide based redox mediator driven 2.2 V high energy density aqueous supercapacitor | |
| Guo et al. | High-performance supercapacitors based on flower-like FexCo3-xO4 electrodes | |
| Luo et al. | Sulfur-deficient flower-like zinc cobalt sulfide microspheres as an advanced electrode material for high-performance supercapacitors | |
| Lv et al. | A novel 3D MnNi2O4@ MnNi2S4 core-shell nano array for ultra-high capacity electrode material for supercapacitors | |
| CN102945758A (en) | Method for preparing electrode material for supercapacitor made from manganese dioxide doped with iron element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190308 Assignee: Hubei Juhui New Material Industry Technology Research Institute Co.,Ltd. Assignor: CENTRAL CHINA NORMAL University Contract record no.: X2022420000147 Denomination of invention: Integrated supercapacitor Granted publication date: 20210914 License type: Common License Record date: 20221228 |